Process of color photography and material therefor



Nov. 7, 1939. J. EGGERT ET AL i 2,179,228

PROCESS OF COLOR PHOTOGRAPHY AND MATERIAL THEREFOR Original Filed March12, 1935 In vemors t By Aorneys a what' T Patented Nov. 7, '1939` UNITEDSTATES PROCESS OF COLOR.'` PHOTOGRAPHY 4 MATERIAL THEREFOR vaNn JohnEggert, Leipzig-Gomis, and Alfred Froehlichk and Bruno Wendt, Dessau,Germany, assignors, l by mesne assignments, to Agfa Ansco Corpora.

tion, Binghamton, N. Y., a corlmration` of Dela- Application March 12,1935, 'serial No. 10,704. Renewed April 11, 1939. In Germany March 16,1934 l5 Claims.

Our present invention relates to color photography.

Une of its objects is to provide an improved process of colorphotography. `Another object is a material for this improved process.Further objects will be seen from the detailed specication followinghereafter.

For the production of colored photographic pictures by color synthesis`by means of azo-dyestuffs there have hitherto been available. twoprincipal procedures. One procedure depends on the use of adiam-component which is not stable towardsr light (diazotype process),whilst in the other use is made of the silverimage in order to produce acolored image by way of a reactive silver compound. Particularly in thelatter case it is endeavoured to incorporate one or both of the dyestuicomponents in the light-V sensitive layer as far as possible in a waterinsoluble, stable form resistant to the development and fixing baths,and in such a manner that the transparency, natural sensitivity andartificial sensitization of the layer are not diminished.v

It has'been proposed, for example, to add the dyestui components to thephotographic layer in the form of compounds insoluble in water, `such asmetal compounds, salts of organic acids'or, in

the case of acid components, in the `formof esters,

anilides or the like. These compounds are to be nely dispersed, forIexample, by introducinginto the gelatin an alcoholic solution of thecompound which is insoluble inwater, so that the' compound isprecipitated in the photographic layer. In this manner it is possible toincorporate the compounds in the gelatin in such a fine state ofdistribution that notwithstanding the insolubility of the compound inwater the gelatin dries to a, transparent layer. .Another procedure foradding dyestuff components to the gelatin in water insoluble form makesuse of coupling components which can be fixed by mordanting. Suchcoupling components, for example, naphthol,

chromotropic acid or the like, can be xed on the gelatin with the aid ofa metal oxide and provided that the component has a suitableconstitution the gelatin will dry to a layer clear as glass.

The present invention is based on the dis covery that it is possible toincorporate in the photographic layer azocomponents from aqueoussolutions in such a manner thatv they are resistant towards the usualphotographic baths by choosing those azo-dyestuff components which havesubstantive properties with respect to the layer. The addition of thesesubstantive comu pounds naturally does not in any way impair the served,since in contrast Vto other processes the compounds are not distributedheterogeneously inthe layer but are actually dissolved in the gelatin.

The' procedure for carrying out the invention may consist for example,in adding to a solution of gelatin or the like a solution of anazo-component or ,diazo-component which is substantive towards gelatin,whereuponthe gelatin is thoroughly washed with water and then worked upin the usualmanner. It is also possible totreat algelatin layer o1 afoil of gelatin with a solution of one ofthe aforesaid dyestuicomponents. ln both cases the gelatin, in the language of the dyeingindustry, is dyed by the dyestuff component even though in the case of acolorless component the layer does not acquire a color which can beperceived by the eye. Y

In order to produce a colored image .use may be made of any'of the knownprocesses.

For instance gelatin which has been rtreated. with Vboth dyestuicomponents may be worked up into a silver halide emulsion. .Afterexposure the silver image is bleached in a bleaching bath which at thesame time tans and hardens the gelatin .atthe exposedparts of the layer.If now the layer is treated with an acidifled solution of sodiumnitrite, Adiasotization and formation of a dyestuif occur at thosepartsof the picture area which are `not hardened and are therefore accessibleto the action of the nitrite solution. ln this manner a red vpicture maybe obtained by means of 2 S-hydroxynaphthoic-acid-a-naphthalidecorresponding with the formula l -COf-NH and `u r e a-bis-(para-aminobenzoyl-para-phenylene-diamine-sulfonic acid correspondingwith the formula Y In this method it is also possible to incorporate inthe gelatin only the eze-component and to use instead of the nitritesolution a diam-solution. Thus by dyeing the gelatin with 2:3-hydroxynnaphthoic-acid-a-naphthalide and treating the layer with tetrazotizeddianisioline there is obtained a blue picture. Another procedure mayconsist in dyeing the gelatin only with the azocomponent and then eitherconverting the silver image into an anti-diazotate image (for vexampleaccording to U. S. Patent No. 1,963,197) or caus- 5 ing the silverhalide to adsorb a diazonium compound and after washing forming thedyestui in a coupling bath. For example, it the gelatin is dyed withdi-ortho-sulfobenzylidene-4:4diami nodiphenylurea corresponding with theformula S 03H B 01H a yellow picture may be obtained by means o! theanti-diazotate of -naphthylamine. Furthermore, there can be used insteadof the 2:3-hydroxynaphthoic acid arylides similarly constitutedhydroxycarboxylic acid amides, for instance, arylides of2:3-hydroxyanthracenic acid, arylides o of hydroxycarbazole carbonioacid, arylides of 0 hydroxynaphthocarbazole carboxylic acid (a. compoundof this group corresponds with the formula C O--NH or arylides ofterephthalacetic acid (a compound of this group corresponds with theformula arylides of the hydroxycarboxylic acid of diphenylene oxide anddiphenylene sulfide (compounds of this group corresponds with theformulae on oom v (Jo-NH@ CEs' on ci s (Jo-NH@ furthermore the arylidesof -naphthindole-2- 50 phenyl-7-hydroxycarboxylic acid (a compound ofthis group corresponds with the formula and as well as pyrazolones fromZ-p-aminophenylthiazoles (a compound of this group corresponds with theformula NBC-CH:

CO- Ha) and 2-hydroxyuoren, -hydroxyanthracen, hy-l droxychrysene andothers. A like picture is obtained ii the silver halide is caused toadsorb para-nitro-benzenediazoniumchloride and coupling is then broughtabout.

Yet a furth'er procedure in accordance with the invention consists indyeing the gelatin with both dyestuff components and then converting thesilver image into an insoluble nitrite compound.

. If now diazotization is brought about in any suit- 10 able manner thedyestufl is formed at the places in the layer corresponding with theimage. In this manner a. red picture may be produced, for example, fromthe urea from para-dimethylaminobenzoyl-para-aminobenzoyl-2-amino--naph-15 thol-'I-sulfonic acid corresponding with the formula Ho,NH-coONn-oo-Omcnm pounds of aminonaphthol sulfonic and carboxylic acids(a compound of this group corresponds with the formula -O-NH-oo-O-Nm) ofnaphthylamine sulfonlc and carboxylic acids (a compound of this groupcorresponds with the formula of cresotinic acid and of diaminocarbazoledisul- 4 ionic acid (a. compound of this group corresponds with theformula HO: N 70 H Ganga as well as the ureas from the amnobenzoylcompounds o! the aforesaid coupling components (a 75 amazes compound ofthis `group corresponds with the H. Oi particular interest areturther4the benzoyl, benzyland benzylidene-compounds of diaminodiphenyl ureas,of diaminodiphenyl-thioureas, of diaminostilbenes, of'benzidines andsimilar compounds (compounds of these groups with the formulae SOsHcorrespond SOaH so i

including compounds containing any substituents in any positions. J

The invention is of particular importance in its application to theproduction of photographs 35 in natural colors. If there are cast insuperimposed relationship emulsions of which each vis sensitized for oneof the primary colors and is dyed with appropriate dyestuff components,the

color synthesis can be conducted in the layers in ample, in the case ofa three-color rllm two color images may be produced on one side of thesupport byI the process of the invention, whereas the remaining colorimage may be produced, for example, on the other side of the support bytoning or on the same side by an imbib-ition process.

The invention comprises a photographic material consisting of a supportcoated on one or both sides with one or more layers of silver halidegelatin emulsion which is or are dyed with an azo-dyestuff component orcomponents substantive with respect to the layer.

The following examples serve to illustrate the invention:

dll

Example 1 A nlm coated with a layer of gelatin is bathed in thefollowing solution:

whereupon the material is Washed with Water for about 1/2 hour. Then thesheet is bathed in a solution of p-diphenylamindiazonium sulfate and isdried. After exposure under an original and treatment with an aqueoussolution of ammonia or gazeous ammonia a blue picture is produced at theplaces which were not illuminated.

Example 2 l There is produced a solution of 10grams ofp-dimethylamidobenzoyl-p-amidobenzoyl-(2-amino-5-naphthol-7-sulfonicacid) in 1000 cc. of water, with the addition of 10 cc. of a causticsodasolution of 20% strength.

In this solution a silver bromide emulsion layer is bathed for 10minutes and washed with water for about 1 hour. An original is printedon this layer, and the layer developed, fixed and the silver imagebleached by means of copper chloride. The bleached-out silver image isconverted into naphthylamine-antidiazotate-si 1v e r 'by means ol analkaline solution of -naphthylamine-antidiazotate-sodium and t h o r o ug h l y Washed.v When this picture is immersed into a solution of 1 gramof citric acid and 1 gram of potassium bromide, a red azo-dye picture isproduced. The silver bromide is removed by fixing.

Y y Example 3 There is made a solution of 20 grams of2.3hydroxynaphthoic-acid--naphthalide in 1000 cc. oi? Water and i l ce.o1 asolution of caustic soda of 20 strength.

The solution is filtered and mixed with a solution of grams ofurea-bis-(p-amidobenzoyl-pphenylenediamine sulionic acid) in a quantityof Water as small as possible and a small amount oi caustic sodasolution; a silver bromide emulsion layer is bathed therein for about 10minutes,

washed with water for about 1 hour and dried.

When printing on this layer and converting the silver image in knownmanner into an insoluble nitrite compound, a red dye picture is producedby starting diazotization by bathing the layer in dilute acetic acid.

Example d l00 cc. of silver bromide emulsion are mixed with a solutionof 0.5 gram of 2.3-hydroxynaphthoic-acid-a-naphthalide in l0 cc. of acaustic soda solution of 5% strength.

Furthermore there is addedl a solution of 0.3 gram ofurea-bis-(p-amldobenaoyl-p h e n yl- The caustic soda is neutralized bymeans of acetic acid the emulsion solidified and washed with water. Theemulsion is cast and the silver image produced in the emulsion layer byprinting, developing and hiring is bleached with a bleaching bath havingthe property to tan the gelatin at the places of the picture. It thepicture is treated with a solution of 5 grams of sodium nitrite in 200cc. of acetic acid of 1% strength, a dye picture is produced from thetwo components at the non-hardened places.

Example 5 (a) l kilo of silver bromide emulsion is mixed with 5 grams of2.3-hydroxynaphthoic-aci d-dianisidine dissolved in cc. of methanol 5cc. of a caustic soda solution of 20% strength and neutralized with 15cc. of acetic acid of 10% strength. This emulsion is sensitized forgreen.

(b) 1 kilo of silver bromide emulsionismixedwith 5 grams of urea from1(3'amidophenyl)3 methyl-5-pyrazo1one by conversion with phosgene 25 cc.of methanol and 5 cc. of caustic soda solution of 20% strength areneutralized with 15 cc. of acetic acid.

lwhich is decolorized in the developer, and a panchromatic silverbromide emulsion is cast on the filter layer. Now a partial colorpicture is produced in each of' the layers, but after development andfixing only that side of the film is bleached to which the two emulsionlayers (a) and (b) have been applied. The bleached-out silver .picturesare converted into -naphthylamineantidiazotate-silver pictures in themanner indicated in Example 1. If these pictures are treated with thesolution of coupling component indicated in Example 1,.a yellow dyepicture is produced in the layer (a) and a red dye picture is producedin the layer (b). The silver picture on the opposite side of the supportis converted into a blue picture by dye-toning, for instance, an ironblue picture.

In the single iigure of the accompanying drawing there is shown aphotographic material accompanying to this invention. The support a isprovided with a photographic layer dyed with a compound havingsubstantive properties with respect thereto.

What we claim is:

1. A process of producing color photographs, which comprisesincorporating in a silver halide gelatin emuisiona coupling component ofan azo dye, said coupling component having a chemical constitution whichimparts to said component substantive properties towards the gelatin,forming a light-sensitive layer from said emulsion, exposing said layerto light controlled by an lobject tobe reproduced, developing the latentsilver image, and causing said coupling component to react with a diazocompound, thereby producing an aZo-dyestuff picture in situ with thesilver picture.

2. A'process of producing color photographs, which-comprises treating asilver halide emulsion layer with a solution of a coupling component ofan azo dye, said coupling component having a constitution which impartsthereto substantive properties towards the gelatin, forming a light-Asensitive layer from said emulsion, exposing said layer to lightcontrolled by an object to be reproduced, developing the latent silverimage, and causing said coupling component to react with a diazocompound, thereby producing an azo-dyestuff picture in situ with thesilver picture.

3. A process of producing color photographs, which comprises treating agelatin solution containing silver halide with a solution of a couplingcomponent having a chemical constitution which imparts theretosubstantive properties with respect to the gelatin, forming alight-sensitive layer from said emulsion, exposing said layer to lightcontrolled by an object to be reproduced, de-

veloping the latent silver image, and causing said coupling component toreact with a diazo compound, thereby producing an azo-dyestui picture insitu with the silver picture.

. 4. A light-sensitive photographic element comprising a support and atleast one silver halide emulsion layer capable of being converted into acolored picture by exposure to light, development and treatment with adiazo compound, said silver halide emulsion layer containing a couplingcomponent of an azo dye; said coupling component having a chemicalconstitution which imparts thereto substantive properties with respectto the l which comprises incorporating in a silver halide gelatinemulsion a diazo compound and a coupling component of an azo dye, saiddiazo compound and said coupling component having a chemicalconstitution which imparts thereto substantive properties towardsgelatin, forming a light-sensitive layer from said emulsion, exposingsaid layer to light controlled by an object to be reproduced, developingand fixing said layer, bleaching said layer in a bath which has at thesame time a tanning and hardening action on the gelatin of the exposedparts of the layer, and treating said layer with an acidiiied solutionof sodium nitrite.

6. A light sensitive material for color photography comprising a supportand a silver halide gelatine emulsion thereon, containing an organiccolorless dyestui component capable of reacting with a further componentto produce a dyestui image, said first component having a chemicalconstitution which imparts thereto substantive properties with respectto the gelatine.

7. A light sensitive material for color photography comprising a supportand a silver halide gelatine emulsion thereon, containing an organiccolorless dyestuff component capable of reacting with a furthercomponent to produce a dyestui image, said first component containing anorganic group which imparts to said component substantive character withrespect to the gelatine.

8. A light sensitive element as defined in claim 6 wherein said rstcomponent contains at least 3 organic rings. l

9. A light sensitive material for color photography comprising asupport, a plurality of silver halide gelatine emulsions carried by saidsupport, each emulsion containing an' organic colorless dyestuicomponent capable of reacting with a further component to produce 'adyestuff image diierent in color from that produced in the other layers,said rst component having a chemical constitution which imparts theretosubstantive properties with respect to the gelatine.

10. A light-sensitive element as defined in claim 6, wherein said iirstcomponent contains at least 3 organic rings, at least 2 of said ringsbeing selected from th class of fused rings and rings connected togetherby a linkage selected from the class consisting of a direct nuclearcarbon to nuclear carbon linkage, a -CH=N- linkage, a -NHCO- linkage, a-NH-CO-HN- linkage, a -NH--CS-NH- linkage, a CH2- NH- linkage and a-CH=CH- linkage.

11. A light-sensitive element as deiined in claim 6, wherein said rstcomponent contains at least 3 organic rings, at least 2 of said ringsbeing fused together.

12. A light sensitive element as defined in claim 6, wherein said iirstcomponent contains at least 3 organic rings, at least one ring beingheterocyclic.

13. A light-sensitive material for color photographycomprising a supportand a silver halide gelatin emulsion thereon containing anhydroxynaphthoic acid arylide containing an organic group which impartsto said compound substantive character with respect to the gelatin.

colorless dyestui componentcapable of reacting with a further componentto produce-a dyestuff image, said first component containing at least 3organic rings, at least 2 of said rings beingselect ed from the class offused rings `and rings vconnected together by a linkageselected from thegroup consisting of a direct lnuclear carbonio nuclear carbon linkage, a-CH==N- linkage, a

linkage and a -CI-I=CH-A linkage, said cornponents although beingsoluble `in aqueous solu` tions being fast to diffusion in the gelatim iJOHN EGGRTQ .ALFRED FROEHLICH. BRUNO WENDT.y

age, a -NH-cs-NH- linkage, a CH2- Nagin

